CN107020374A - A kind of Ti3SiC2The preparation method of/Cu composite conductive powders - Google Patents
A kind of Ti3SiC2The preparation method of/Cu composite conductive powders Download PDFInfo
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- CN107020374A CN107020374A CN201710403789.9A CN201710403789A CN107020374A CN 107020374 A CN107020374 A CN 107020374A CN 201710403789 A CN201710403789 A CN 201710403789A CN 107020374 A CN107020374 A CN 107020374A
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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Abstract
A kind of Ti disclosed by the invention3SiC2The preparation method of/Cu composite conductive powders：Its step is：Step 1, to Ti3SiC2Powder carries out alcohol and washes, is roughened, being sensitized, activating, washing and drying and processing successively, obtains pre-processing Ti3SiC2Powder；Step 2, utilize CuSO4·5H2O、EDTANa2, NaOH and 2 2' bipyridyls make copper electrolyte；Step 3, using the copper electrolyte made through step 2 to the pretreatment Ti that is obtained through step 13SiC2Powder carries out plating；Step 4, through after step 3, being filtered to remaining material after plating, carry out drying and processing to filtering remaining part after liquid, obtain Ti3SiC2/ Cu composite conductive powders.The Ti obtained using the preparation method of the present invention3SiC2/ Cu composite conductive powders have relatively low density, good stability and high conductivity.
Description
Technical field
The invention belongs to conductive material or electric slurry preparation method technical field, and in particular to a kind of Ti3SiC2/ Cu is multiple
Close the preparation method of conductive powder body.
Background technology
With the development of electronic technology, increasing electronic device develops towards the direction of flexibility, such as：Intellectual garment
Dress, robot skin, rollable e-book, strain transducer, stretchable solar cell etc..At present, extensively should
Conducting film is prepared on the hard backing materials such as glass ceramics more, and it is crisp, frangible and not that hard backing material has matter
Yielding the shortcomings of, its application is greatly limit, the demand of electronic equipment of new generation can not be met, thus it is new
Flexible conducting material need exploitation badly.
Conductive filler plays conclusive effect to the electric conductivity of material.From the point of view of the report of existing literature, flexibility is led
Electric material it is main with metal nanometer line, graphene, CNTs etc. for conductive filler, but be due to high cost, complicated technique,
Or can not carry out producing in batches etc. the limitation of factor, still there is a certain distance from practical application.Therefore, develop functional, low
Cost, the conductive filler of energy volume production become particularly significant.
Ti3SiC2Novel tertiary lamellar compound is that current research is widest, most representational Mn+1AXnPhase material
(wherein M is transition metal, and A is III or IV major element, and X is C or N).Ti3SiC2Material is typical conductivity ceramics, is not only had
There are the ceramic characteristics such as high intensity, high rigidity, good heat endurance, anti-oxidant, corrosion-resistant, while also having metal leading well
Heat, conductive and easy processing characteristic, are with a wide range of applications.By Ti3SiC2Conduction is made after being combined with traditional conductive material
Filler, on the one hand can reduce the density of material, while can also remain in that excellent electric conductivity.
The content of the invention
It is an object of the invention to provide a kind of Ti3SiC2The preparation method of/Cu composite conductive powders, what is prepared is compound
Conductive powder body has relatively low density, good stability and high conductivity.
The technical solution adopted in the present invention is, a kind of Ti3SiC2The preparation method of/Cu composite conductive powders, specifically according to
Following steps are implemented：
Step 1, to Ti3SiC2Powder carries out alcohol and washes, is roughened, being sensitized, activating, washing and drying and processing successively, obtains pre-
Handle Ti3SiC2Powder；
Step 2, utilize CuSO4·5H2O、EDTANa2, NaOH and 2-2'- bipyridyls make copper electrolyte；
Step 3, using the copper electrolyte made through step 2 to the pretreatment Ti that is obtained through step 13SiC2Powder is plated
Cover processing；
Step 4, through after step 3, being filtered to remaining material after plating, to filtering remaining part after liquid
Drying and processing is carried out, Ti is obtained3SiC2/ Cu composite conductive powders.
The features of the present invention is also resided in：
Step 1 is specifically implemented according to following steps：
Step 1.1, the Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；
Step 1.2, by the Ti in step 1.13SiC2Powder is poured into ethanol water, and makes Ti3SiC2Powder soaks completely
Not in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 10min~30min；
Step 1.3, by the Ti through being obtained after step 1.23SiC2Powder is poured into hydrofluoric acid aqueous solution, and makes Ti3SiC2Powder
Body is totally submerged in hydrofluoric acid aqueous solution, using hydrofluoric acid aqueous solution to Ti3SiC2Powder carries out roughening treatment, during roughening treatment
Between be 30min~60min；
Step 1.4, by volume be 1~4：1 by hydrochloric acid and SnCl2The aqueous solution is mixed, and forms sensitized treatment liquid, will be through step
The Ti obtained after rapid 1.33SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid,
Using sensitized treatment liquid to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 30min~60min；
Step 1.5, in mass ratio be 1：1：1 by PdCl2The aqueous solution, boric acid aqueous solution and mixed in hydrochloric acid, form activating solution,
By the Ti through being obtained after step 1.43SiC2Powder is poured into activating solution, and makes Ti3SiC2Powder is totally submerged in activating solution, profit
With activating solution to Ti3SiC2Powder carries out activation process, and the activation process time is 1h~2h；
Step 1.6, first with deionized water to the Ti through being obtained after step 1.53SiC2Powder is cleaned, then successively through centrifugation, mistake
Filter is handled, and drying and processing is carried out afterwards, obtains pre-processing Ti3SiC2Powder.
In step 1.2：It is 1 by volume by second alcohol and water that ethanol water, which is,：1~3 it is well mixed after obtain；
In step 1.3：It is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：1~4 it is well mixed after obtain；In step
1.4 in：SnCl2The concentration of the aqueous solution is 10g/L~20g/L, and the concentration of hydrochloric acid is 100ml/L~200ml/L；In step 1.5
In：PdCl2The concentration of the aqueous solution is 0.1g/L~0.2g/L, and the concentration of boric acid aqueous solution is 10g/L~20g/L, hydrochloric acid it is dense
Spend for 100ml/L~200ml/L.
In step 1.6：Wash number is 2 times~4 times, and the temperature control of drying and processing is 80 DEG C~100 DEG C.
Step 2 is specifically implemented in accordance with the following methods：
In under normal temperature condition, in the following order and proportioning mixes each raw material, copper electrolyte is made：
Wherein, 11~13 are adjusted to by adding NaOH by pH value of solution.
Step 3 is specifically implemented according to following steps：
Step 3.1, the pretreatment Ti that will be obtained through step 13SiC2Powder is added in the copper electrolyte made through step 2,
Form mixed material；
Wherein, Ti is pre-processed3SiC2Powder and Cu mass ratio are 1~4：1；
Step 3.2, the mixed material obtained through step 3.1 is placed in the water-bath that temperature is 50 DEG C~80 DEG C and enters water-filling
Bath heating, while formaldehyde is added dropwise into mixed material with continuous stirring carries out electroless copper reaction, and adds in this course
Plus the pH value that NaOH remains whole reaction system disappears, plating terminates more than 11 up to blue in whole reaction system.
In step 4：Drying and processing uses vacuum drying chamber, and temperature control is 80 DEG C~120 DEG C.
The beneficial effects of the present invention are：
(1) Ti of the invention3SiC2The preparation method of/Cu composite conductive powders, Ti is prepared by electroless plating method3SiC2/
Cu conductive powder bodies, during which without to Ti3SiC2Powder is completely coated, and effect formation conductive network can be oozed by Chongqing, can be effective
Improve the electric conductivity of material；
(2) Ti of the invention3SiC2The preparation method of/Cu composite conductive powders, energy while material conductivity is not reduced
Cu content is reduced, the density of material on the one hand can be reduced, on the other hand can reduce the cost of material；
(3) Ti of the present invention is utilized3SiC2The Ti that the preparation method of/Cu composite conductive powders is obtained3SiC2/ Cu composite guides
Electric powder has good chemical stability, can be used under certain high temperature and corrosive environment；
(4) Ti of the invention3SiC2The preparation method of/Cu composite conductive powders, technological process is simple, cost is low and energy
Production.
Brief description of the drawings
Fig. 1 is the Ti obtained using the preparation method of the present invention3SiC2The XRD of/Cu composite conductive powders；
Fig. 2 is the Ti obtained using the preparation method of the present invention3SiC2The SEM figures of/Cu composite conductive powders.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of Ti of the present invention3SiC2The preparation method of/Cu composite conductive powders, specifically implements according to following steps：
Step 1, to Ti3SiC2Powder carries out alcohol and washes, is roughened, being sensitized, activating, washing and drying and processing successively, obtains pre-
Handle Ti3SiC2Powder, specifically implements according to following steps：
Step 1.1, the Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；
Step 1.2, by the Ti in step 1.13SiC2Powder is poured into ethanol water, and makes Ti3SiC2Powder soaks completely
Not in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 10min~30min；
Wherein, it is 1 by volume by second alcohol and water that ethanol water, which is,：1~3 it is well mixed after obtain；
Step 1.3, by the Ti through being obtained after step 1.23SiC2Powder is poured into hydrofluoric acid aqueous solution, and makes Ti3SiC2Powder
Body is totally submerged in hydrofluoric acid aqueous solution, using hydrofluoric acid aqueous solution to Ti3SiC2Powder carries out roughening treatment, during roughening treatment
Between be 30min~60min；
Wherein, it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：1~4 it is well mixed after obtain；
Step 1.4, by volume be 1~4：1 by hydrochloric acid and SnCl2The aqueous solution is mixed, and forms sensitized treatment liquid, will be through step
The Ti obtained after rapid 1.33SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid,
Using sensitized treatment liquid to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 30min~60min；
Wherein, SnCl2The concentration of the aqueous solution is 10g/L~20g/L, and the concentration of hydrochloric acid is 100ml/L~200ml/L；
Step 1.5, in mass ratio be 1：1：1 by PdCl2The aqueous solution, boric acid aqueous solution and mixed in hydrochloric acid, form activating solution,
By the Ti through being obtained after step 1.43SiC2Powder is poured into activating solution, and makes Ti3SiC2Powder is totally submerged in activating solution, profit
With activating solution to Ti3SiC2Powder carries out activation process, and the activation process time is 1h~2h；
Wherein, PdCl2The concentration of the aqueous solution is 0.1g/L~0.2g/L, and the concentration of boric acid aqueous solution is 10g/L~20g/
L, the concentration of hydrochloric acid is 100ml/L~200ml/L；
Step 1.6, first with deionized water to the Ti through being obtained after step 1.53SiC2Powder is cleaned 2 times~4 times, then successively
Through centrifugation, filtration treatment, carry out drying and processing under the conditions of 80 DEG C~100 DEG C, obtain pre-process Ti3SiC2Powder.
Step 2, utilize CuSO4·5H2O、EDTANa2, NaOH and 2-2'- bipyridyls make copper electrolyte, specific method is such as
Under：
In under normal temperature condition, in the following order and proportioning mixes each raw material, copper electrolyte is made：
Wherein, 11~13 are adjusted to by adding NaOH by pH value of solution.
Step 3, using the copper electrolyte made through step 2 to the pretreatment Ti that is obtained through step 13SiC2Powder is plated
Processing is covered, is specifically implemented according to following steps：
Step 3.1, the pretreatment Ti that will be obtained through step 13SiC2Powder is added in the copper electrolyte made through step 2,
Form mixed material；
Wherein, Ti is pre-processed3SiC2Powder and Cu mass ratio are 1~4：1；
Step 3.2, the mixed material obtained through step 3.1 is placed in the water-bath that temperature is 50 DEG C~80 DEG C and enters water-filling
Bath heating, while formaldehyde (HCHO) is added dropwise into mixed material with continuous stirring carries out electroless copper reaction, and in this mistake
The pH value that addition NaOH remains whole reaction system in journey, until blueness disappears in whole reaction system, is plated more than 11
Cover end.
Step 4, through after step 3, being filtered to remaining material after plating, to filtering remaining part after liquid
Drying and processing is carried out, Ti is obtained3SiC2/ Cu composite conductive powders；
Wherein, drying and processing uses vacuum drying chamber, and temperature control is 80 DEG C~120 DEG C.
The Ti that the preparation method of the present invention is prepared3SiC2The insulating body such as/Cu composite conductive powders and resin, rubber
Mixed by a certain percentage, by adjusting Ti3SiC2The content of/Cu composite conductive powders, can prepare electric conductivity good
Conductive film material；In addition, Ti3SiC2/ Cu composite conductive powders can also be used as the conductive filler of electric slurry.
Fig. 1 is Ti3SiC2The XRD of/Cu composite conductive powders, as can be seen from Figure 1：Except Ti3SiC2Diffraction maximum
Outside, moreover it is possible to substantially observe Cu diffraction maximum, illustrate to be successfully prepared Ti3SiC2/ Cu composite conductive powders；
Fig. 2 is Ti3SiC2The SEM figures of/Cu composite conductive powders, as can be seen from Figure 2：Nanometer Cu particles are attached to
Ti3SiC2Powder surface, but not complete cladding Ti3SiC2Powder.
Embodiment 1
The Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；By Ti3SiC2Powder pours into ethanol
(it is 1 by volume by second alcohol and water that ethanol water is to the aqueous solution：1 it is well mixed after obtain) in, and make Ti3SiC2Powder
It is totally submerged in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 10min；By alcohol
The Ti obtained after washing3SiC2Powder pours into hydrofluoric acid aqueous solution, and (it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：1
Obtained after well mixed) in, and make Ti3SiC2Powder is totally submerged in hydrofluoric acid aqueous solution, utilizes hydrofluoric acid aqueous solution pair
Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is 30min；It is 1 by volume：4 by hydrochloric acid, (concentration of hydrochloric acid is
100ml/L) and SnCl2The aqueous solution (SnCl2The concentration of the aqueous solution is 10g/L) mixing, sensitized treatment liquid is formed, by roughening treatment
The Ti obtained afterwards3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, using quick
Change treatment fluid to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 60min；It is 1 in mass ratio：1：1 by PdCl2Water
Solution (PdCl2The concentration of the aqueous solution is 0.1g/L), boric acid aqueous solution (concentration of boric acid aqueous solution is 10g/L) and hydrochloric acid (salt
The concentration of acid is 100ml/L) mixing, form activating solution, the Ti that will be obtained after sensitized treatment3SiC2Powder is poured into activating solution, and
Make Ti3SiC2Powder is totally submerged in activating solution, using activating solution to Ti3SiC2Powder carries out activation process, activation process time
For 2h；With deionized water to the Ti that is obtained after activation3SiC2Powder clean 2 times, then successively through centrifugation, filtration treatment, after 80
Drying and processing is carried out under the conditions of DEG C, obtains pre-processing Ti3SiC2Powder；
In under normal temperature condition, in the following order and ratio mixes raw material, copper electrolyte is made：
Also to be adjusted to 11 by adding NaOH by pH value of solution；
Ti will be pre-processed3SiC2Powder is added in copper electrolyte, forms mixed material, pre-processes Ti3SiC2Powder and Cu's
Mass ratio is 4：1；It is to carry out heating water bath in 50 DEG C of water-bath that mixed material is placed in into temperature, at the same with continuous stirring to
Formaldehyde (HCHO) is added dropwise in mixed material and carries out electroless copper reaction, and addition NaOH remains whole body in this course
The pH value of system is more than 11, until blueness disappears in whole system, plating terminates；
Remaining system after plating is filtered, drying and processing is carried out to filtering remaining material after liquid, adopts
With vacuum drying chamber, temperature control is 80 DEG C, obtains Ti3SiC2/ Cu conductive powder bodies.
Embodiment 2
The Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；By Ti3SiC2Powder pours into ethanol
(it is 1 by volume by second alcohol and water that ethanol water is to the aqueous solution：1.5 it is well mixed after obtain) in, and make Ti3SiC2Powder
Body is totally submerged in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 15min；Will
The Ti that alcohol is obtained after washing3SiC2Powder pours into hydrofluoric acid aqueous solution, and (it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：
2 it is well mixed after obtain) in, and make Ti3SiC2Powder is totally submerged in hydrofluoric acid aqueous solution, utilizes hydrofluoric acid aqueous solution pair
Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is 40min；It is 1 by volume：3 by SnCl2The aqueous solution (SnCl2Water
The concentration of solution is 12g/L) and hydrochloric acid (concentration of hydrochloric acid is 120ml/L) mixing, sensitized treatment liquid is formed, after roughening treatment
Obtained Ti3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, utilizes sensitization
Treatment fluid is to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 50min；It is 1 in mass ratio：1：1 by PdCl2It is water-soluble
Liquid (PdCl2The concentration of the aqueous solution is 0.15g/L), boric acid aqueous solution (concentration of boric acid aqueous solution is 12g/L) and hydrochloric acid (hydrochloric acid
Concentration be 120ml/L) mixing, formed activating solution, the Ti that will be obtained after sensitized treatment3SiC2Powder is poured into activating solution, and is made
Ti3SiC2Powder is totally submerged in activating solution, using activating solution to Ti3SiC2Powder carries out activation process, and the activation process time is
1.5h；With deionized water to the Ti that is obtained after activation3SiC2Powder clean 3 times, then successively through centrifugation, filtration treatment, after 85
Drying and processing is carried out under the conditions of DEG C, obtains pre-processing Ti3SiC2Powder；
In under normal temperature condition, in the following order and ratio mixes raw material, copper electrolyte is made：
Also to be adjusted to 11 by adding NaOH by pH value of solution；
Ti will be pre-processed3SiC2Powder is added in copper electrolyte, forms mixed material, pre-processes Ti3SiC2Powder and Cu's
Mass ratio is 3：1；It is to carry out heating water bath in 60 DEG C of water-bath that mixed material is placed in into temperature, at the same with continuous stirring to
Formaldehyde (HCHO) is added dropwise in mixed material and carries out electroless copper reaction, and addition NaOH remains whole body in this course
The pH value of system is more than 11, until blueness disappears in whole system, plating terminates；
Remaining system after plating is filtered, drying and processing is carried out to filtering remaining material after liquid, adopts
With vacuum drying chamber, temperature control is 90 DEG C, obtains Ti3SiC2/ Cu conductive powder bodies.
Embodiment 3
The Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；By Ti3SiC2Powder pours into ethanol
(it is 1 by volume by second alcohol and water that ethanol water is to the aqueous solution：2 it is well mixed after obtain) in, and make Ti3SiC2Powder
It is totally submerged in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 20min；By alcohol
The Ti obtained after washing3SiC2Powder pours into hydrofluoric acid aqueous solution, and (it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：
2.5 it is well mixed after obtain) in, and make Ti3SiC2Powder is totally submerged in hydrofluoric acid aqueous solution, utilizes hydrofluoric acid aqueous solution
To Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is 45min；It is 1 by volume：2 by SnCl2The aqueous solution (SnCl2
The concentration of the aqueous solution is 15g/L) and hydrochloric acid (concentration of hydrochloric acid is 150ml/L) mixing, sensitized treatment liquid is formed, by roughening treatment
The Ti obtained afterwards3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, using quick
Change treatment fluid to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 45min；It is 1 in mass ratio：1：1 by PdCl2Water
Solution (PdCl2The concentration of the aqueous solution is 0.17g/L), boric acid aqueous solution (concentration of boric acid aqueous solution is 15g/L) and hydrochloric acid (salt
The concentration of acid is 150ml/L) mixing, form activating solution, the Ti that will be obtained after sensitized treatment3SiC2Powder is poured into activating solution, and
Make Ti3SiC2Powder is totally submerged in activating solution, using activating solution to Ti3SiC2Powder carries out activation process, activation process time
For 1.5h；With deionized water to the Ti that is obtained after activation3SiC2Powder clean 3 times, then successively through centrifugation, filtration treatment, after
Drying and processing is carried out under the conditions of 90 DEG C, obtains pre-processing Ti3SiC2Powder；
In under normal temperature condition, in the following order and ratio mixes raw material, copper electrolyte is made：
Also to be adjusted to 11 by adding NaOH by pH value of solution；
Ti will be pre-processed3SiC2Powder is added in copper electrolyte, forms mixed material, pre-processes Ti3SiC2Powder and Cu's
Mass ratio is 2：1；It is to carry out heating water bath in 70 DEG C of water-bath that mixed material is placed in into temperature, at the same with continuous stirring to
Formaldehyde (HCHO) is added dropwise in mixed material and carries out electroless copper reaction, and addition NaOH remains whole body in this course
The pH value of system is more than 11, until blueness disappears in whole system, plating terminates；
Remaining system after plating is filtered, drying and processing is carried out to filtering remaining material after liquid, adopts
With vacuum drying chamber, temperature control is 100 DEG C, obtains Ti3SiC2/ Cu conductive powder bodies.
Embodiment 4
The Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；By Ti3SiC2Powder pours into ethanol
(it is 1 by volume by second alcohol and water that ethanol water is to the aqueous solution：2.5 it is well mixed after obtain) in, and make Ti3SiC2Powder
Body is totally submerged in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 25min；Will
The Ti that alcohol is obtained after washing3SiC2Powder pours into hydrofluoric acid aqueous solution, and (it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：
3 it is well mixed after obtain) in, and make Ti3SiC2Powder is totally submerged in hydrofluoric acid aqueous solution, utilizes hydrofluoric acid aqueous solution pair
Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is 35min；It is 1 by volume：1 by SnCl2The aqueous solution (SnCl2Water
The concentration of solution is 18g/L) and hydrochloric acid (concentration of hydrochloric acid is 180ml/L) mixing, sensitized treatment liquid is formed, after roughening treatment
Obtained Ti3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, utilizes sensitization
Treatment fluid is to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 35min；It is 1 in mass ratio：1：1 by PdCl2It is water-soluble
Liquid (PdCl2The concentration of the aqueous solution is 0.18g/L), boric acid aqueous solution (concentration of boric acid aqueous solution is 18g/L) and hydrochloric acid (hydrochloric acid
Concentration be 180ml/L) mixing, formed activating solution, the Ti that will be obtained after sensitized treatment3SiC2Powder is poured into activating solution, and is made
Ti3SiC2Powder is totally submerged in activating solution, using activating solution to Ti3SiC2Powder carries out activation process, and the activation process time is
2h；With deionized water to the Ti that is obtained after activation3SiC2Powder clean 4 times, then successively through centrifugation, filtration treatment, after 95 DEG C
Under the conditions of carry out drying and processing, obtain pre-process Ti3SiC2Powder；
In under normal temperature condition, in the following order and ratio mixes raw material, copper electrolyte is made：
Also to be adjusted to 11 by adding NaOH by pH value of solution；
Ti will be pre-processed3SiC2Powder is added in copper electrolyte, forms mixed material, pre-processes Ti3SiC2Powder and Cu's
Mass ratio is 1：1；It is to carry out heating water bath in 75 DEG C of water-bath that mixed material is placed in into temperature, at the same with continuous stirring to
Formaldehyde (HCHO) is added dropwise in mixed material and carries out electroless copper reaction, and addition NaOH remains whole body in this course
The pH value of system is more than 11, until blueness disappears in whole system, plating terminates；
Remaining system after plating is filtered, drying and processing is carried out to filtering remaining material after liquid, adopts
With vacuum drying chamber, temperature control is 110 DEG C, obtains Ti3SiC2/ Cu conductive powder bodies.
Embodiment 5
The Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；By Ti3SiC2Powder pours into ethanol
(it is 1 by volume by second alcohol and water that ethanol water is to the aqueous solution：3 it is well mixed after obtain) in, and make Ti3SiC2Powder
It is totally submerged in ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 30min；By alcohol
The Ti obtained after washing3SiC2Powder pours into hydrofluoric acid aqueous solution, and (it is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：4
Obtained after well mixed) in, and make Ti3SiC2Powder is totally submerged in hydrofluoric acid aqueous solution, utilizes hydrofluoric acid aqueous solution pair
Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is 30min；It is 1 by volume：1 by SnCl2The aqueous solution (SnCl2Water
The concentration of solution is 20g/L) and hydrochloric acid (concentration of hydrochloric acid is 200ml/L) mixing, sensitized treatment liquid is formed, after roughening treatment
Obtained Ti3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, utilizes sensitization
Treatment fluid is to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 30min；It is 1 in mass ratio：1：1 by PdCl2It is water-soluble
Liquid (PdCl2The concentration of the aqueous solution is 0.2g/L), boric acid aqueous solution (concentration of boric acid aqueous solution is 15g/L) and hydrochloric acid (hydrochloric acid
Concentration be 200ml/L) mixing, formed activating solution, the Ti that will be obtained after sensitized treatment3SiC2Powder is poured into activating solution, and is made
Ti3SiC2Powder is totally submerged in activating solution, using activating solution to Ti3SiC2Powder carries out activation process, and the activation process time is
1h；With deionized water to the Ti that is obtained after activation3SiC2Powder clean 4 times, then successively through centrifugation, filtration treatment, after 100
Drying and processing is carried out under the conditions of DEG C, obtains pre-processing Ti3SiC2Powder；
In under normal temperature condition, in the following order and ratio mixes raw material, copper electrolyte is made：
Also to be adjusted to 11 by adding NaOH by pH value of solution；
Ti will be pre-processed3SiC2Powder is added in copper electrolyte, forms mixed material, pre-processes Ti3SiC2Powder and Cu's
Mass ratio is 1：1；It is to carry out heating water bath in 80 DEG C of water-bath that mixed material is placed in into temperature, at the same with continuous stirring to
Formaldehyde (HCHO) is added dropwise in mixed material and carries out electroless copper reaction, and addition NaOH remains whole body in this course
The pH value of system is more than 11, until blueness disappears in whole system, plating terminates；
Remaining system after plating is filtered, drying and processing is carried out to filtering remaining material after liquid, adopts
With vacuum drying chamber, temperature control is 120 DEG C, obtains Ti3SiC2/ Cu conductive powder bodies.
In fact, a kind of electroless copper of invention disclosed patent prepares Cu/Ti3SiC2The method of composite
(CN1419985A) by the method for chemical plating in Ti in3SiC2Particle surface is prepared for the Cu clads of densification, afterwards with Cu powder
It is mixed with Ti3SiC2The enhanced Cu based composites of particle, are mainly used as electrical contact material.And Ti of the present invention3SiC2/ Cu is led
In electric raw powder's production technology, material is to be attached to Ti by Cu particles3SiC2On the Ti not coated completely that is formed3SiC2/Cu
Conductive powder body, is essentially different in the preparation method, performance and purposes of material with existing technology.
A kind of Ti of the present invention3SiC2The preparation method of/Cu composite conductive powders, the Ti prepared by electroless plating method3SiC2/
Cu composite conductive powders, it is not necessary to Ti3SiC2Powder is completely coated, and effect formation conductive network can be oozed by Chongqing, is improved
The electric conductivity of material；While material conductivity is not reduced, the density and cost of material can be reduced；In addition, preparing
Ti3SiC2/ Cu composite conductive powders have good chemical stability, can be used under certain high temperature and corrosive environment.
Utilize Ti of the present invention3SiC2The preparation method of/Cu composite conductive powders, the Ti prepared3SiC2/ Cu composite conductings
There is powder relatively low density (to be far below Cu 8.9g/cm3), good chemical stability and heat endurance (can 400 DEG C with
Used in lower temperature range) and high conductivity (resistivity be less than 10-7Ω·m)。
Claims (7)
1. a kind of Ti3SiC2The preparation method of/Cu composite conductive powders, it is characterised in that specifically implement according to following steps：
Step 1, to Ti3SiC2Powder carries out alcohol and washes, is roughened, being sensitized, activating, washing and drying and processing successively, is pre-processed
Ti3SiC2Powder；
Step 2, utilize CuSO4·5H2O、EDTANa2, NaOH and 2-2'- bipyridyls make copper electrolyte；
Step 3, using the copper electrolyte made through step 2 to the pretreatment Ti that is obtained through step 13SiC2Powder is carried out at plating
Reason；
Step 4, through after step 3, being filtered to remaining material after plating, carried out to filtering remaining part after liquid
Drying and processing, obtains Ti3SiC2/ Cu composite conductive powders.
2. Ti according to claim 13SiC2The preparation method of/Cu composite conductive powders, it is characterised in that the step 1
Specifically implement according to following steps：
Step 1.1, the Ti for taking average granularity to be more than 93% for 2 μm~20 μm, purity3SiC2Powder；
Step 1.2, by the Ti in step 1.13SiC2Powder is poured into ethanol water, and makes Ti3SiC2Powder be totally submerged in
Ethanol water, using ethanol water to Ti3SiC2Powder carries out alcohol and washed, and alcohol washes the time for 10min~30min；
Step 1.3, by the Ti through being obtained after step 1.23SiC2Powder is poured into hydrofluoric acid aqueous solution, and makes Ti3SiC2Powder is complete
Hydrofluoric acid aqueous solution is immersed in entirely, using hydrofluoric acid aqueous solution to Ti3SiC2Powder carries out roughening treatment, and the roughening treatment time is
30min~60min；
Step 1.4, by volume be 1~4：1 by hydrochloric acid and SnCl2The aqueous solution is mixed, and forms sensitized treatment liquid, will be through step 1.3
The Ti obtained afterwards3SiC2Powder is poured into sensitized treatment liquid, and makes Ti3SiC2Powder is totally submerged in sensitized treatment liquid, using quick
Change treatment fluid to Ti3SiC2Powder carries out sensitized treatment, and the sensitized treatment time is 30min~60min；
Step 1.5, in mass ratio be 1：1：1 by PdCl2The aqueous solution, boric acid aqueous solution and mixed in hydrochloric acid, form activating solution, will be through
The Ti obtained after step 1.43SiC2Powder is poured into activating solution, and makes Ti3SiC2Powder is totally submerged in activating solution, utilizes work
Change liquid to Ti3SiC2Powder carries out activation process, and the activation process time is 1h~2h；
Step 1.6, first with deionized water to the Ti through being obtained after step 1.53SiC2Powder is cleaned, then successively through centrifugation, at filtering
Reason, carries out drying and processing afterwards, obtains pre-processing Ti3SiC2Powder.
3. Ti according to claim 23SiC2The preparation method of/Cu composite conductive powders, it is characterised in that in the step
In rapid 1.2：It is 1 by volume by second alcohol and water that ethanol water, which is,：1~3 it is well mixed after obtain；
In the step 1.3：It is 1 by volume by hydrofluoric acid and water that hydrofluoric acid aqueous solution, which is,：1~4 it is well mixed after obtain
's；
In the step 1.4：SnCl2The concentration of the aqueous solution is 10g/L~20g/L, the concentration of hydrochloric acid for 100ml/L~
200ml/L；
In the step 1.5：PdCl2The concentration of the aqueous solution is 0.1g/L~0.2g/L, and the concentration of boric acid aqueous solution is 10g/L
~20g/L, the concentration of hydrochloric acid is 100ml/L~200ml/L.
4. Ti according to claim 23SiC2The preparation method of/Cu composite conductive powders, it is characterised in that in the step
In rapid 1.6：Wash number is 2 times~4 times, and the temperature control of drying and processing is 80 DEG C~100 DEG C.
5. Ti according to claim 13SiC2The preparation method of/Cu composite conductive powders, it is characterised in that the step 2
Specifically implement in accordance with the following methods：
In under normal temperature condition, in the following order and proportioning mixes each raw material, copper electrolyte is made：
Wherein, 11~13 are adjusted to by adding NaOH by pH value of solution.
6. Ti according to claim 13SiC2The preparation method of/Cu composite conductive powders, it is characterised in that the step 3
Specifically implement according to following steps：
Step 3.1, the pretreatment Ti that will be obtained through step 13SiC2Powder is added in the copper electrolyte made through step 2, is formed
Mixed material；
Wherein, Ti is pre-processed3SiC2Powder and Cu mass ratio are 1~4：1；
Step 3.2, the mixed material obtained through step 3.1 is placed in carries out water-bath in the water-bath that temperature is 50 DEG C~80 DEG C and add
Heat, while formaldehyde is added dropwise into mixed material with continuous stirring carries out electroless copper reaction, and is added in this course
NaOH remains the pH value of whole reaction system more than 11, until blueness disappears in whole reaction system, plating terminates.
7. Ti according to claim 13SiC2The preparation method of/Cu composite conductive powders, it is characterised in that in the step
In rapid 4：Drying and processing uses vacuum drying chamber, and temperature control is 80 DEG C~120 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108633242A (en) * | 2018-04-11 | 2018-10-09 | 西安工程大学 | A kind of titanium carbon/nickle composite powder radio-radar absorber and preparation method |
| CN109133932A (en) * | 2018-07-10 | 2019-01-04 | 西安工程大学 | Ramie fabric SiC/Cu material preparation method based on precast body method of impregnation |
| CN113429820A (en) * | 2021-06-25 | 2021-09-24 | 西安热工研究院有限公司 | Oriented Mxene/Co conductive filler for anti-corrosion coating and preparation method thereof |
| CN114605894A (en) * | 2022-04-11 | 2022-06-10 | 西安热工研究院有限公司 | Based on AgNWs/Ti3AlC2Corrosion-resistant coating of conductive filler and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419985A (en) * | 2001-11-21 | 2003-05-28 | 中国科学院金属研究所 | Method for mfg. Cu/Ti3SiC2 composite material by chemical copper plating |
| CN101343700A (en) * | 2008-08-25 | 2009-01-14 | 倪树春 | Ag/Ti3SiC2 electric contact material and manufacturing process |
| CN101345143A (en) * | 2008-08-25 | 2009-01-14 | 倪树春 | Cu/Ti3SiC2 electric contact material and preparation technique |
| CN104946922A (en) * | 2015-06-05 | 2015-09-30 | 山东正诺集团有限公司 | Preparation method for Ti3SiC2-Al automobile brake disc material |
-
2017
- 2017-06-01 CN CN201710403789.9A patent/CN107020374B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419985A (en) * | 2001-11-21 | 2003-05-28 | 中国科学院金属研究所 | Method for mfg. Cu/Ti3SiC2 composite material by chemical copper plating |
| CN101343700A (en) * | 2008-08-25 | 2009-01-14 | 倪树春 | Ag/Ti3SiC2 electric contact material and manufacturing process |
| CN101345143A (en) * | 2008-08-25 | 2009-01-14 | 倪树春 | Cu/Ti3SiC2 electric contact material and preparation technique |
| CN104946922A (en) * | 2015-06-05 | 2015-09-30 | 山东正诺集团有限公司 | Preparation method for Ti3SiC2-Al automobile brake disc material |
Non-Patent Citations (1)
| Title |
|---|
| 张中宝等: "Ti_3SiC_2陶瓷颗粒表面超声波化学镀铜", 《金属功能材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108633242A (en) * | 2018-04-11 | 2018-10-09 | 西安工程大学 | A kind of titanium carbon/nickle composite powder radio-radar absorber and preparation method |
| CN109133932A (en) * | 2018-07-10 | 2019-01-04 | 西安工程大学 | Ramie fabric SiC/Cu material preparation method based on precast body method of impregnation |
| CN113429820A (en) * | 2021-06-25 | 2021-09-24 | 西安热工研究院有限公司 | Oriented Mxene/Co conductive filler for anti-corrosion coating and preparation method thereof |
| CN113429820B (en) * | 2021-06-25 | 2022-04-26 | 西安热工研究院有限公司 | Oriented Mxene/Co conductive filler for anti-corrosion coating and preparation method thereof |
| CN114605894A (en) * | 2022-04-11 | 2022-06-10 | 西安热工研究院有限公司 | Based on AgNWs/Ti3AlC2Corrosion-resistant coating of conductive filler and preparation method thereof |
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